Thermoplastic compositions and method of preparing the same



Patented Apr. 13, 1937 THERMOPLASTIC COMPOSITIONS AND .METHOD OF PREPARING THE SAME Henry Jacobsen (now by judicial decree to Henry Jenett), Englewood, N. J., assignor to Celancse Corporation of America, a corporation of Delaware I No Drawing. Application May 18, 1933,

, Serial N0. 671,642

11 Claims. ('01. 106-40)- This invention relates to the preparation of thermoplastic compositions comprising derivaw Elves of cellulose and rubber in intimate admixure.

An object-of my invention is to form compositions of matter that may be shaped under heat and pressure to any desired form, which compositions of matter comprise a derivative of cellulose compound in intimate admixture with rubber. A

further object of my invention is to iorm such compositions of matter by simultaneously grinding and dispersing the derivative 0! cellulose and the rubber in aliquid medium that is a non-solvent or precipitant for the derivative of cellulose. Other-objects of this invention will be described in detail.

Heretofore rubber and cellulose derivatives have been considered incompatible, since it is practically impossible to combine them by prior known I methods even on a laboratory scale, due to the lack of suitable common solvents. I

In my copending U. S. applications Serial No. 641,233 filed Nov. 4, 1932 and Serial No. 663,344 filed March 29, 1933, of which this application is in part a continuation, I have disclosed processes that are suitable for compounding thermoplastic materials from a chlorinated rubber base and I have also described, by way 01' example, a plastic mass containing such substituted compound of rubber.

I have found that if cellulose derivatives and rubber are simultaneously ground and dispersed in the presence of a liquid medium that has no solvent action on the cellulose derivatives, homogeneous and intimate mixtures are formed, which have the desirable physical and chemical properties of both the cellulose derivatives and the rubber. Plasticizers, resins, oils, pigments, dyes, filling materials and the like may be incorporated 40 to impart any desired physical properties to such compositions.

Compositions formed by my invention have many desirable properties. The rubber content increases the chemical 'inertness of the cellulose derivatives; it improves the resiliency and flexibility of the product; it increases the softening point, as well as the melting-point, of the composition; it makes the product more waterproof and ore water-repellent; it lends to the compound 5 /greater adhesiveness to cloth, paper and similar bases. On the other hand, the cellulose derivatives, by surroundingkthe rubber with a fine pm- I tective coating, appean to make it-more resistant to the oxidizing influence of the atmosphere; they 55 remove the tackiness that is characteristic of unvulcanized rubber; they improve the flow of rubber compounds under heat and pressure and, in the case of very low melting rubbers, such as guttapercha or balata, they increase the softening andmelting points very considerably. 5

Any suitable rubber may be employed in car- 'rying out my invention. The term rubber as employed herein is not only intended to cover all .kinds of natural rubber of the empirical formula (C1oH1e)X derived from the sap of such plants 10 as Hevea, Ficus, Castilloa, Manihot, etc. as well as those of the Sapotazea and Minusops families known as guttapercha and balata respectively, but it is also intended to includesynthetic substances of analogous compositions, such as poly- 15 merized hydrocarbons oi the isoprene series, for instance.

The rubber may be incorporated with any suitable derivatives of cellulose such as cellulose nitrate or organic derivatives of cellulose. The 20 organic derivatives may be organic esters of cellulose such as cellulose acetate, cellulose iormate, cellulose propionate or cellulose butyrate, or cellulose ethers such as ethyl cellulose, methyl cellulose and benzyl cellulose. These cellulose 25 derivatives may, prior to treatment, be in the form of flocks, grains, flakes, fibres, granules and thelike. I

While the rubber, with or without modifyin agents, is preferably ground and dispersed in the 3 liquid non-solvent medium simultaneously with the cellulose derivative, in some cases the rubber may be added after such cellulose derivative has been ground and dispersed in the non-solvent liquid. 35

In order to obtain the required grinding and dispersing, it is important to employ apparatus suitable for this-purpose. This maybe accomplished for instance by forcing a suspension of the cellulose derivative and rubber in water or 40 other non-solvent liquid medium between two closely spaced abrasive surfaces, such surfaces being either moved rapidly in opposite directions, or one surface moving rapidly while the other is 1 stationary, thus producing a great attrition eflect. 45

A convenient apparatus for causing this grinding and dispersing is a colloid mil} having two 'discs that have opposing abrasive surfaces.

These discs may be rotated in opposite direction at relatively high speeds, or, one disc may be maintained stationary while the other may be caused to rotate rapidly. At least the-surfaces of such discs should be made of abrasive or hard, rough material, such as carborundum,-"sintered corundum, fritted glass, emery, or roughened steel or other hard metal. These discs'may be made wholly of such abrasive material, or. their opposing surfaces may be merely coated or lined with the same. A suitable apparatus that may be media a colloidmillcomprising afstationary disc of carborundum, through the center of which the suspension to be ground and dispersed is fed into the very narrow space between such sta tionary carborundum dlscahd an opposingcatborundum disc rotating at s ay 2500 to 5000 R. P. M.

The use of discs of such ab stsive surfaces in the colloid mill is of great importance, since if the ordinary discs of smooth, fluted or grooved metallic surfaces are employed, it is not possible to attain the best results because of lack of proper grinding action.

The use of a liquid dispersing medium such he water, for instance, which, being a non-solvent,

or precipitant for the derivatives of cellulose, prevents the agglomeration or coalescence of the mechanically homogenized particles keeps the compound in a form suitable for any kind of application, without further chemical or mechanical treatment, except that of preferably, but not necessarily, removing the liquid dispersing medium by evaporation or other known methods of dehydration. Y

Any desired modifying. agent for the thermoplastic composition may be incorporated therewith. By modifying agent I mean any substance which is adapted to impart any desired properties "such as softness, elasticity, flexibility, hardness, gloss, color, stability, etc. to the huished product. Such modifying agents may be incorporated the cellulose'aeetate-or other derivative,v of cellulose and the rubber to form a composition that is capable of producing upon the application of heat and pressure, products that The proceal and product of \peri'ectly homogeneous plastic compound in ex-- plasticizers, dyes, pigments, lakes, filling mate-v rials, resins, oils, etc. Examples of plasticizers are camphor, dibutyl phthalate, diethyl phthalate, tricresyl phosphate, triphenyl phosphate, ethyl paratoluene sulfonamid, etc., the choice of plasticizer depending upon ,the properties of the thermoplastic compound employed as the base.

The amount of non-solvent liquid employed during thegrinding and dispersing will vary in accordance with the nature of the ingredients and the purposefor which the productis intended, so that the product may have a consistency varying from astifl paste to a freely flowing slurry". In the case of the use of water as the non-solvent liquid, the amount employed may be from less than 5 to 12, or more volumes of water per volume of the solid ingredients employed.

' The rubber may be introduced during or after the process of dispersing and grinding of the derivative of cellulose together with all the other desired ingredients. While I prefer to'use a concentrated latex ofapproximately 50% to rubber content, the use of dilute latex or other collodial solutions of rubber, or oi dry rubber,such as can be commercially obtained in the form of crepe; sheet, block, or granule, for instance, will produce excellent results. In the case of a dry natural rubber or of a synthetic rubber, I prefer to reduce the material to a more or less fine grain, which will enable it to pass conveniently through the colloid mill. 'If desired, the natural or synthetic rubber may be added in the form of a solution in some organic solvent medium such as benzol', which is not a solvent of the particular cellue lose derivative employed in the composition.

-If'desired, ruins, such as shellac, or oils such as linseed oil, whichheretofore have been considered to be incompatible with cellulose acetate or other-organic derivatives of my b9 tremely finely divided form.

r the paste or slurry is formed by the combined\ persing and grinding action, this may be wor up into the desired product by several methods, examples of which will nowbe given. In one mode of procedure, the slurry or paste containing the derivative of cellulose, rubber and water or other non-solvent liquid medium. is applied directly to the article or surfaceathat is to be impregnated or covered with the thermoplastic compound. Thus for instance paper or fibre board may be covered with a layer of the plastic composition inslurry or paste form, the liquid dispersing medium, such as water, may be evaporated while the paper or fibre base pass'esthrough the drying machine in a paper'mill, after-which by the use of hot calenders ,or stacks the thermoplastic. composition is fused, thus forming a wateror grease-proof coating, or imparting to the paper or board any other desired properties or finishes, according to the substances employed in making such slurry or paste.

Whiletheuseofsuchslurryorpaste isofimportance in connection with paper making, since it renders possible the conversion or coating of the paper as a part of the routine paper-making process,asagainstadistinctandseparateoperation heretofore applied to the finished paper, it is the inven- 1 tion presents many distinct advantages over prior.)

tobeunderstoodthatsuchslurryor'pastemaybe used for the production or coating of,other mate- -theslurrydirectlytothefabricbase,givinginone operation a coating of any desired thickness, as the absence of volatile solvents for the derivatives of cellulose permits of the applicationoi' even a i very' heavy layer of the thermoplastic compound. such as would require from 3 to 10 or more coatings by the ordinary method of spreading or spraying'solutions of cellulose derivative compositions.

A further important use of such "slurry" is for products. Such a slurry. when made in a liquid medium that has a certainamnity for textile the treatment of fabrics. yarns or other textile fibres, that is compatible with water-soluble sizes I and that is not aifected by the moisture contents,

of the fabric, may be easily applied at the textile mill,eitherasapermanentsisingoraaaflnishing coat, thereby eliminating conversion steps in separate mills. I A second mode oi employing the composition formed by the dispersion and grinding of the derivative of cellulose and rubber in the nonsolvent medium, is partioiuarly useful when memoisture would be objectionable, the dispersing medium of the slurry is first removed by any suitable method, such as spray-drying or drying in a vacuum. The fine powder resulting from the evaporation of the water or non-solvent medium is applied to the smooth surface of the metal,

asbestos board, leather and the like and welded thereto by means of heat and pressure.

In the case where solid bodies are to be formed directly from the thermoplastic composition, either of the two methods above described may be employed, depending upon the product, the

type of equipment available and other factors.

Thus, for instance, thin films or tissue-like transparent or opaque foil may be produced from a slurry on equipment and by means similar to those employed in the paper making industry, while bulky pieces such as molded insulation, novelties, etc., should preferably be made from the plastic composition in dry form, in order to save the time required toevaporate the dispers- V ing medium from each individual articlebefore curing or fusing the plastic composition. The

product formed after removal of the, water or other non-solvent liquid may be used as a molding powder in any suitable manner such as by heating the same until it isflowable and then extruding into a mold, or by placing the powder in a mold and then applying heat and pressure.

In order further to illustrate my invention, but

without being limited thereto, the following specific examples are given merely by way of illustration and are in no way limitative.

Example I The following is an example of a method of making a composition to be used for application to a fabric to form artificial leather.

Parts by weight Cellulose acetate 100 Trlacetin -a Ethyl paratoluene sulfonamid 40 Triphenyl phosphate 30 Latex (50%" 'ibber content) 60 Chrome gr'e 80 The following is an example of a method of making a molding composition suitable for insulators.

Parts by weight Cellulose aceta 100 Diethyl phthalate 18 Ethyl paratoluene sulfonamid C; 12

Triphenyl phosphate 5 Rubber (in solid grain form) 25 Powdered asbestos are suspended in 500 partsby weight of water;

This mixture is subjected to the dispersing and 75 grinding action described in Example I. The resuiting mass is then freed of water by evaporation in. any suitable manner and the dry powder formed may be subjected to heat and pressure in any desired molding operation to form the de sired articles. 5

It is to be understood that the foregoing-dctailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of my invention. j 10 Having described my invention, what I desire to secure by Letters Patent is: 1. In the manufacture of thermoplastic compositions, the step of dispersing and grinding rubber and a derivative of cellulose in solid form in a 15 liquid medium which is a non-solvent for the derivative of cellulose and rubber.

2. In the manufacture of thermoplastic compositions, the step of dispering and grinding rubber latex, having a rubber content of from 50 to 60%, 20 and a derivative of cellulose in solid form in a liquid medium which is anon-solvent for the derivative ofcellulose and rubber.

3. In the manufacture of thermoplastic compositions, the step'of dispersing and grinding rubher and cellulose acetate in solid form in a liquid medium which is a non-solvent for the cellulose acetate and rubber by passing the same between relatively moving closely spaced abrasive surfaces. 30

4. In the manufacture of thermoplastic compositions, the step of dispersing and grinding a derivative of cellulose in solid form, rubber and a modifying agent in a liquid medium which is a non-solvent for the rubber and derivative of cellulose by passing the same between .relatively moving closely spaced. abrasive surfaces.

5. In the manufacture of thermoplastic com positions, the step of dispersing and grinding cellulose acetate in solid form, rubber and a plasticizer for the cellulose acetate in a liquid medium which is a non-:solvent both for the cellulose .ace-

tate and the rubber by passingthe same between relatively moving closely spaced abrasive surfaces. 6. In the manufacture of thermoplastic compositions, the step of dispersing and grinding celluose acetate in solid form and rubber in water by passing the same between relatively moving closely spaced abrasive surfaces. r 7. Process of producing athermoplastic composition comprising dispersing and grinding a de-. rivative of cellulose insolid form and rubber latex, having a rubber content of from 50 to 60%,

in a volatile liquid medium that is'a non-solvent for the derivative of cellulose and rubber, and

'then removing at least part of the volatile nonsolvent liquid medium.

8. Process of producing a thermoplastic composition comprising dispersing and grinding rubber 60 and a derivative of cellulose in solid formina volatile liquid medium that is a non-solvent both for I the derivative of cellulose and the rubber by pass ing the same between relatively moving closely spaced abrasive surfaces, and then removing at 65 least part of the volatile non-solvent liquid medium.

9. Process of producing a thermoplastic composition comprising dispersing and grinding rubber latex, having a rubber content of from 50 to 70 60%, and a water-insoluble derivative of cellulose in solid form in water by passing the same between relatively moving closely spaced abrasive surfaces, and then removing at least part of the, water. 75

4 010,701 10. The process comprising dispersing and grinding rubber and a water-insolubie derivative grinding rubber and a derivative of cellulose in 01' cellulose in solid form in water by passing the solid form in a volatile li'quidmedium that is a same between relatively moving closely spaced non-solvent for, the derivative of cellulose and abrasive surfaces, removing at least part of the 5 rubber, evaporating the liquid medium, applying water and subjecting the massto pressure be- 5 the resulting product to a base and then applytween heated surfaces. 7 ing heat and pressure. HENRY JACOBSEN.

'11. The process comprising dispersing and 

